Coupled peroxides

ABSTRACT

A new class of compounds: R-W-R&#39;&#39; where R and R&#39;&#39; are identical oxy radicals containing peroxide functions such as dialkyl or diaralkyl peroxide, peroxyketal, peroxyester, or monoperoxycarbonate, and W is a carbonyl group, or carbonyl containing group, or an alkylidene or aralkylidene group, or a phosphorus containing group. Examples: Di(1,3-dimethyl-3-(t-butylperoxy)butyl) carbonate; Di(1,3-dimethyl-3-(n-butoxycarbonylperoxy)butyl) carbonate; 2,2-Bis(3,3-di(t-butylperoxy)butoxy) propane; Di(1,3-dimethyl-3-(t-butylperoxy)butyl) ethyl phosphate. They are free radical affording compounds useful in crosslinking of polyolefins and unsaturated polymers, and for the polymerization of vinyl monomers and diolefinic monomers.

United States Patent 191 DAngelo et al.

[ Nov. 5, 1974 COUPLED PEROXIDES [75] Inventors: Antonio Joseph DAngelo, Buffalo;

Orville Leonard Mageli; Chester Stephen Sheppard, both of Kenmore, all of NY.

[73] Assignee: Pennwalt Corporation, Philadelphia,

[22] Filed: Mar. 16, 1973 [21] Appl. No.: 342,106

Related US. Application Data [62] Division of Ser. No. 737,359, June 17, 1968, Pat. No.

[52] US. Cl... 260/94.9 GA, 260/46.5 R, 260/47 X, 260/75 T, 260/77.5 R, 260/785 C, 260/80 C, 260/80.78, 260/82.3, 260/83.3, 260/83.5,

260/92.8 A, 260/92.8 R, 260/93.5 R,

[51] Int. Cl C08f l/60, C08f 27/00 [58] Field of Search 260/94.9 GA, 93.7

[56] References Cited UNITED STATES PATENTS 3,344,126 9/1967 Witman 260/79.5

Stivers 260/41 Stevens et al. 260/453 R Primary Examiner-William H. Short Assistant ExaminerE. A. Nielsen [57] ABSTRACT ethyl 2 Claims, No Drawings 1 PLE EROXIDES This is a continuation division, of application Ser.

No. 737,359, filed June 17, 1968 (now U.S. Pat. No. 725,455).

BACKGROUND OF THE INVENTION 1. The Field of the Invention This invention relates to peroxides obtainable by the coupling of hydroxide group containing peroxides. Particularly the invention relates to coupled peroxide containing one or more carbonyl groups or an alkylidene group in the portion of the molecule which forms the linkage between the two peroxy containing portions of the coupled peroxide molecule. Also the invention relates to methods for preparing such coupled peroxides.

2. Description of the Prior Art No prior art is known with respect to the coupled peroxides of the invention.

U.S. Pat. No. 3,236,872 discloses dialkyl peroxides containing hydroxyl groups, e.g., 2-metliyl-2(tbutylperoxy)-4-pentanol.

A copending application Ser. No. 569,030, filed Aug. 1, 1966 (now U.S. Pat. No. 3,542,856) discloses peroxyesters containing hydroxyl groups, e.g., t-butylperoxy- 3-hydroxypropionate.

Still other precursors, hydroxy substituted peroxyketals are disclosed in a copending application, Ser. No. 727,336 filed May 7, 1968, e.g 3,3-Bis(t-butylperoxt y)-l-butanol.

SUMMARY OF THE INVENTION It has been discovered that high purity polyfunctional peroxides, i.e., at least two peroxy groups, can be prepared by a coupling reaction carried out on a hydroxy group containing peroxide.

The novel polyfunctional peroxides of this invention have the general formula:

where l. R and R are identical, and each contains at least one peroxy group selected from the class consisting of:

where R and R each fall into the same member (i)-(vi) espect vely and th R1, .Rz, R3, R4 R R and R requirfiti I0 be present in the particular R is the same as he correspond ng radical lie. RI R2, R3, 4, and R as the case may be] required to be present in the corresponding R. To illustrate; If R is:

he R is als R1, R2, n ,R' are iden cal in both R and R.

2 W is a diradical selected from the class consisting a 3. R and R are aliphatic having 1-12 carbon atoms, cycloaliphatic having 3-12 carbon atoms, or aromatic ha ing a bon atoms;

4. R is aliphatic or cycloaliphatic, each having 4-10 carbon atoms and the carbon atom joined to the peroxy oxygen atom is a tertiary carbon atom;

5. R is-aliphatic having l-10 carbon atoms or cycloal phati ha ing 3-12 carbon atoms;

R5 is lowe alky ycloalky a alky a y koxy, ycloal o y aralkoxy or arylox 7. R i H or lower alkyl;

8- Y s th dir-adical .0, S, o R6;

9. R is an aliphatic iradical a ng a b atoms or a cycloaliphatic diradical having 3-12 carbon toms;

10. R3 is ipha ic diradical hav ng a bon atoms y oa inhatic i adica ha ing carbon atoms, or aromatic d radica having ca b atoms; I

1 1. R, and R8 are selected from the class consisting of H, alkyl of l l 0 carbons andcycloalkyl of 3-12 carbons and when R, is H, R can also be aryl of 6-12 carbons and R and R can together form an alkylene biradical of 2-11 carbons; and

12. R is a diradical selected from the class consisting of R3 (ii) YR Y (iii) 0 R I JYR YiBR YR Yi JYRWi JYR Y YR Y R lYR Y YRM iYR Yi JRW (vii) 0 0 YR YR iiYR Y (viii) 0 YR3YH3YR3Y Ethylene Bis[ l,3-dimethyl-3-(t-butylperoxy)-butyl carbonate].

Di[ l,3-dimethyl 3-(t-butylperoxy)butyl] ethyl phosphate.

2,2-Bis[3 ,3-di(t-butylperoxy)butoxy]propane. N,N'-m-phenylene bis[O-[ 1,3-dimethyl-3-(tbutylperoxy)butyl]carbomate].

A DESCRIPTION OF THE INVENTION AND EXAMPLES The aliphatic radical includes substitution by aryl radicals araliphatic radicals and cycloaliphatic radicals. The cycloaliphatic radical includes substitution by aliphatic and by aryl radicals. The aromatic and aryl radicals may be substituted by aliphatic and by cycloaliphatic radicals; Both cycloaliphatic, aromatic and aryl radicals may be single ring, such as phenyl and cyclohexyl, or connected rings, such as biphenyl, binaphthyl, bicyclopropyl, bicyclopentyl, or fused rings such as napthyl, decahydrona'phthyl. It is to be understood that the substituents should not interfere with the desired coupling reaction. In general halogen, ester, ether, thioether, and carbonate substituents or groups containing these do not interfere; Desirably R R R R R R and R contain only carbon and hydrogen Commonly R is alkyl or alkoxy having l-6 carbon atoms; cycloalkyl or cycloalkoxy having a total of 3-12 carbon atoms; aralkyl or aralkoxy having 7-12 carbon atoms aryl or aryloxy having 6:12 carbon atoms.

commonlylRsis H ta kylha in lsarbeitatszms- .Commonly R and R are each H or alkyl having 1-4 carbon atoms or one can bearyl while the other is H 2? B1 and B g jqthet 2a". szrm. an alkylsnsbitadisa R is an aliphatic or cycloaliphatic radical, each having 4-l0 carbon atoms, affording a t-carbon atom which is joined to a peroxy oxygen a tom; or ex ample.

The described coupled peroxy compounds are effective crosslinking agents for polymeric materials which are capable of being crosslinked to form a thermoset material.

Illustrative classes of polymeric materials where these new peroxy compounds are effective include: homopolymers, such as poly(vinyl chloride) and polyolefins (e.g. polyethylene and polybutenes); elastomers, such as natural rubber and synthetic rubber (e.g. butyl rubber, GR-S rubbers, neoprene, acrylic rubber, Buna rubber, ethylene-propylene rubber, silicone rubbers, and miscellaneous elastomeric material such as polybutene-styrene copolymers and urethane rubber), copolymers such as polylethylene-vinyl acetate) and condensation polymers such as polyamides, polyesters (both saturated and unsaturated) and polycarbonates. The polymer may contain a plasticizer and/or oil extenders and/or fillers such as carbon black, silica and calcium carbonate. Also they are effective in curing (crosslinking) mixtures of vinyl monomers and unsaturated polyesters.

Also they are effective for the polymerization, to form solid polymers, of unsaturated monomers capable of polymerization by a free radical mechanism. For example, vinyl monomers such as vinyl halides; vinylidene halides; vinyl esters such as vinyl acetate and vinyl stearate; the vinyl toluene; the acrylics such as acrylic acid, methyl methacrylate and ethyl acrylate. Other monomers are: The styrene-butadiene blends for rubber copolymers; styreneacrylonitrile blends for copolymers; fluoroethylenes and chloro-fluorethylenes; butadiene; isoprene and similar polymerizable dienes.

UTILITY AND DISCUSSION These novel coupled peroxycompounds can be utilized in the following ways:

I. They can crosslink polyethylene, polyethylenepolypropylene rubber, polyolefin elastomers, urethane rubbers, silicon rubber etc. (Example XIII, Tables I, II, III and IV) 2. They can polymerize monomers containing polymerizable ethylenic grouping. (Example XIV) 3. They can cure resins curable by free radical producing agents. (Example XV) 4. They can be used as free radical sources and/or catalysts in organic syntheses and applications where free radicals are required.

Some of the desirable properties that a peroxide has to have to be useful for crosslinking polyethylene are: low volatility, high thermal stability, and good efficiency with respect to its active oxygen content.

The volatility and the thermal stability are necessary requisites, since the peroxide has to tolerate the high temperatures of the milling operation, which is a necessary step to incorporate the peroxide with the polymer before the crosslinking process. If the peroxide is too volatile (asin the case of di-t-butyl peroxide) there would not be any peroxide left for the crosslinking process at the end of the milling step. lf the peroxide is not volatile, but its thermal stability is low, a premature decomposition of the peroxide will take place during the milling step, which results in a premature crosslinking of the polymer. If this happens, the polymer cannot be shaped or formed any further since the thermoplastic polymer has become thermoset too soon.

Efficiency is another property that a good crosslinking peroxide has to have in order to make the crosslinking process economical and effective.

Another advantage of the difunctional peroxides obtained by the coupling reaction is that they utilize their active oxygen content to the full extent. Some of the known commercial difunctional peroxides like 2,5- dimethyl-2,5-di(t-butylperoxy)hexane and 2,5- dimethyl-2,5-di(t-butylperoxy)-hexyne-3 are not as efficient in utilizing their active oxygen content as the difunctional peroxide of our invention (see Table l). This is an unexpected result.

We have demonstrated that hydroxy containing peroxides, such as 2-methyl-2-(t-butylperoxy)-4-pentanol, do not have all the desirable properties of a good crosslinking agent. lts volatility is low and its thermal stability is good, but its efficiency is poor. (see Table I) By coupling this hydroxy containing peroxide, using the process described in Examples, I, ll, and III, we found the coupled product to be an exceptionally good crosslinking agent possessing all the desirable properties. (see Table l) [The half-life of the coupled products (e.g. from Examples I, II, III, and V) is almost double that of the hydroxy containing peroxide precursor. This, to say the least, is unexpected] (see Example XVI) [Another advantage of the coupling reaction is the simplicity of preparing pure difunctional peroxides without gqng through tedious purification steps that are necessary when they are prepared peroxidizing difunctional intermediates] The coupling reaction is not the only expedient one can use to improve volatility of the hydroxy containing peroxides. One can acylate the hydroxyl group with a sufficiently high molecular weight acylating agent and the volatility will be reduced. Using too low of a molecular weight acylating agent will not lower volatility sufficiently unless the starting hydroxy-containing peroxide is already of substantial molecular weight.

The disadvantage of this approach is that an increase in the molecular weight of the peroxide is attained at aa9rifi9e QfEEEELQELEPREQQPQPI:

Peroxides are sold by the pound and used according to the active oxygen content. So, if one had to buy a high molecular weight product with small active oxygen content, larger amounts of the product would have to be used to obtain the desired results in that particu- The coupled compounds of our invention minimize this disadvantage, since they'gave the desirable properties without excessively increasing the molecular w h Thus, the coupling reactions of hydroxy-containing i peroxides RH, afford novel peroxides, RWR,

that are unexpectedly more stable than RH; more cfficient than RH and other commercial diperoxides; and at the same time are less volatile than RH and simple derivatives of RH.

, PREPARATION The hydroxy-containing peroxide precursors, RH, can be prepared by peroxidation of intermediates containing hydroxyl groups, either primary or secondary, or by hydrolysis or reduction of ester-containing peroxides.

The novel peroxides, RW-R', of this invention may be prepared by reacting the hydroxy-containing peroxides, RH, with hydroxy coupling agents such as phosgene, diacid chlorides, bischloroformates, diisocyanates, dichlorophosphonates, aldehydes, and ketals.

The novel peroxides of this invention may be prepared by one or more of the following methods.

Method 1 (The One Step Process) Two moles of the hydroxy-containing peroxide are reacted with one mole of the desired hydroxy-coupling i flll i fiiii i l reactions are:

One mole of the hydroxy-containing peroxide is first reacted with one mole of hydroxy coupling agent to atn an atsameiatsp d s The preparation of certain of these intermediate products is disclosed in copending application Ser. No. 727,323 filed May 7, 1968 (now US. Pat. No. 3,671,651)

This intermediate product can subsequently be reacted with another mole of the hydroxy-containing peroxide in a second step to form R--W-R'. l s tiye.rsastismsarsa.

g 1) tort-amine 2R C1 0 RCER CO2 HCI The reaction conditions depend upon the characteristics of the reactants and peroxy products. In general the intermixing of the coupling agent and the peroxy compound is carried out from about -l0C. to +25C., and then the reaction temperature may be increased to a maximum'of not more than 100C., to allow the reaction to go to completion. Preferably the maximum reaction temperature should be not more than about 60C.

The reactions may take place in the presence or absence of an inert diluent or solvent. In certain cases, where one or more of the reactants are solids, such a diluent is necessary to provide intimate contact of the reactants; in other cases the diluent provides an additional safety factor, as some pure products are hazardous.

In certain cases the presence of a base may be necessary i.e. Method I (i), (ii), (iii), and (iv) or Method II (a), and (0 Any compound, inorganic or organic in nature, which functions as an acid acceptor (base) for the acid by-product of the reaction can be used.

Illustrative of organic bases are: pyridine, and substituted pyridines; lower alkyl tertiary amines such as trimethyl amine, and triethylamine; dimethyl aniline; and N-methyl-2-pyrrolidone.

Illustrative inorganic bases which can be used are the basic salts of alkali metals and alkaline earth metals such as sodium, and potassium carbonates, and sodium and potassium hydroxide.

The above methods of preparation of the novel peroxides, R-WR', are further illustrated in Examples I to XII.

EXAMPLE 1 Preparation of Di[ I,3-dimethyl-3-( t-butylperoxy)butyl] carbonate butylperoxy)-4-pentanol (84 percent) and 15.8 g. (0.2 mole) of pyridine in 50 ml. of hexane cooled to 5:: 1C. was added a solution of 5 g. (0.05 mole) of phosgene in 50 ml. of hexane.

The addition vwas made at such a rate that the reaction temperature could be controlled at 51*: 1C. After the addition was completed, the reaction temperature was allowed to rise to 23-25C., and then raised to 50: 1C. by means of external heating. The reaction mixture was allowed to react for 48 hours at this temperature.

The reaction mixture was filtered from the pyridine hydrochloride and the organic phase washed with 10 percent tartaric acid solution and water to neutrality.

The organic phase was then dried over anhydrous magnesium sulfate, filtered and the solvent evaporated under reduced pressure. A slightly colored liquid was obtained, 20.1 g., theoretical 20.3 g. The infrared spectrum (I.R.) of this material showed presence of trace amounts of unreacted 2-methyl-Z-(t-butylperoxy)-4- pentanol.

The unreacted material was distilled under reduced pressure at 34-35C. and .05 mm. of Hg. The IR. of the residue was free of OH and contained the characteristic bands of the desired product.

EXAMPLE II Preparation of [A] After the addition was completed, the mixture was allowed to reflux for twenty-four hours at 36: 1C. At the end of this period the reaction mixture was filtered from the pyridine hydrochloride and washed with 10 percent solution of tartaric acid and water to neutrality. The ether solution was dried over anhydrous MgSO filtered and the solvent evaporated under reduced pressure and then under vacuum at 0.1 mm of Hg and a bath temperature of 60 to C. A liquid was obtained (4 0 g. theoretical yield 40.6 g H I The IR. of this liquid was free of OH and C-Cl bands and contained the characteristic bands of the desired product.

9 EXAMPLE 11] Preparation of [A] To a solution of 29.2 g. (0.1 mole) of 1,3-dimethyl-3- (t-butylperoxy)butyl chloroformate (86.5 percent) in diethyl ether at 23: 1C. was added a solution of 7.9 g. (0.1 mole) of pyridine in 10 ml. of diethyl ether. To this mixture was added dropwise 0.6 g. of H at such a rate that the evolution of CO could be controlled to a reasonable rate. The reaction temperature rose to about 30C. The reaction mixture was allowed to react at room temperature (23C.) until the CO evolution ceased (24 hours). The reaction mixture was diluted with H 0 and theorganic phase was separated, washed with 10 percent solution of tartaric acid and H 0 to neutrality.

The ether solution was dried over anhydrous MgSO filtered and the solvent evaporated under reduced pres-- sure and then under vacuum at 0.1 mm. of Hg. and a bath temperature of 6070C. A liquid was obtained 16.2 g.; theoretical yield 20.3 g.

The IR. of this material was free of OH and CCl bands and contained the characteristic bands of the de- To a mixture of 8.0 g. (0.0295 mole) of 4,4-di(tbutylperoxy)-5-pentanol (97.3 percent), 2.4 g. (0.0295 mole) of pyridine in 50 m1. diethyl ether cooled at 5:

1C. was added a solution of 1.45 g. (0.0147 mole) of phosgene in 25 ml. of diethyl ether. After the addition was completed, the reaction mixture was allowed to stir for six hours at 23: 1C. After this time, the pyridine hydrochloride was filtered off and the ether solution was washed with percent solution of tartaric acid and water to neutrality. The ether phase was dried over anhydrous MgSO filtered and the solvent evaporated under reduced pressure. A liquid was obtained, 8.5 g.

The IR. indicated that the desired product was obtained.

EXAMPLE V Preparation of Di[2-(t-butylperoxycarbonyl)ethyl] carbonate CH3 0 O CH: cH.-l:-oo CH2"'CH20 -o-crn-cm-b-oob-orn To a mixture of 17.4 g. (0.1 mole) of t-butyl 3-hydroxyperoxypropionate (93 percent) and 7.9 g. (0.1 mole) of pyridine in diethyl ether cooled at 5: 1C. was added a solution of 30.5 g. (0.1 mole) of 2-(tbutylperoxycarbonyl)ethyl chloroformate (75 percent) in 50 ml. of diethyl ether.

After the addition was completed the reaction mixture was allowed to stir for one hour at 30: 1C. At the end of this period the reaction mixture was filtered off from the pyridine hydrochloride and the ether solution was washed with 10 percent solution tartaric acid and water to neutrality. The ether solution was dried over anhydrous MgS0 filtered and the solvent evaporated under reduced pressure. A colorless liquid was obtained (41 g.). The LR. of this material showed the characteristic bands for the desired product.

EXAMPLE VI Preparation of 3 Di[ 1 ,3-dimethyl-3-(n-butoxycarbonylperoxy)-butyl] b nats.

CH3 CH: 0 CH1 (3H3 To a mixture of 26.0 g. (0.1 mole) of 0,0-( 1,1- dimethyl-3-hydroxybutyl) O-butyl monoperoxycarbonate percent) and 7.9 g. (0.1 mole) of pyridine in 50 ml. of diethyl ether, cooled at 10 1C. was added a solution of 31.4 g. (0.1 mole) of 1,3-dimethyl-3-(nbutoxycarbonyl-peroxy)butyl chloroformate in 50 ml. of diethyl ether, at such a rate that the reaction could be controlled at 10: 1C.

After the additionwas completed, the reaction temperature was allowed to rise 2325C. and allowed to stir for 1 hour. At the end of this time, the reaction mixture was diluted with water and the organic phase separated and washed with 10 percent solution of tartaric acid and water to neutrality. The ether phase was dried over anhydrous magnesium sulfate, filtered and the solvent evaporated under reduced pressure and then under vacuum at 30 to 35C. and 0.05 mm. of Hg. A liquid was obtained, 45.3 g.

The [.R. of this material indicated that the desired product was prepared.

EXAMPLE Vll Preparation of Di[ l,3 dimethyl-3-(t-butylperoxy)butyl] succinate A mixture of 4.13 g. (0.02 mole) of 2-methyl-2-(tbutylperoxy)-4-pentanol (92 percent) and 1.5 g. (0.01 mole) of succinyl chloride and 25 ml. of diethyl ether was refluxed for 48 hours.

Evolution of hydrochloric acid could be detected as the mixture was refluxing. At the end of 48 hours no more HCl could be detected.

The mixture was stripped under reduced pressure. A slightly yellow colored liquid was obtained weighing 4.4 g.; theoretical yield 4.42 g.

The I.R. of this material was free of OH and C-Cl bands and contained the characteristic bands of the desired product.

EXAMPLE Vlll Preparation of Ethylene Bis[ l ,3-dimethyl-3-(t-butylperoxy)butyl carbonate] To a mixture of 29.4 g. (0.1 mole) of 1,3-dimethyl-3- (t-butylperoxy)butyl chloroformate (86.3 percent) and 3.6 g. (0.05 mole) of ethylene glycol in 26 ml. of acetone and 25 ml. of diethyl ether at 20: 1C. was added a solution of 7.9 g. (0.1 mole) of pyridine in 10 ml. of diethyl ether. The mixture was allowed to react for 24 hours at 25: 1C. At the end of this period the reaction mixture was filtered off from the pyridine hydrochloride and the organic phase washed with 100 ml. 10 percent solution of tartaric acid and water to neutrality. The ether solution was dried over anhydrous MgSO filtered and the solvent evaporated under reduced pressure.

A yield of 15.2 g. was obtained. The I.R. ofthis material showed the characteristic bands of the desired compound with little contamination of hydroxylcontaining material.

EXAMPLE lX Preparation of Di[ 1,3-dimethyl-3-(t-butylperoxy)butyl] ethyl phosphate on. on, cm 1in crn- CH: 1 o-vo-(1-orn( crn 0 1r 12115 11 o 0 o C(CH3)3 C(CI'I3)3 To a mixture of 22.1 g. (0.1 mole) of 2-methyl-2-(tbutylperoxy)-4-pentanol (86 percent) and 7.9 g. (0.1 mole) of pyridine in 50 ml. of diethyl ether cooled at St 1C. was added a solution of 8.14 g. (0.05 mole) of ethyl dichlorophosphonate in 10 ml. of diethyl ether.

After the addition was completed the reaction mixture was allowed to stir at 25i 1C. for 24 hours.

At the end of this time the reaction mixture was filtered from the pyridine hydrochloride and it was washed with 10 percent solution of tartaric acid and water to neutrality. The ether solution was dried over anhydrous MgSO filtered and the solvent evaporated under reduced pressure. A liquid was obtained (13 g.). The l.R. indicated that the desired product was prepared.

EXAMPLE X Preparation of N,N'-m-phenylene bis[ l,3-dimethyl-3-(t-butylperoxy)butyl carbonate] A mixture of 4.2 g. (0.02 mole) of 1,3-dimethyl-3-(tbutylperoxy)butanol (91 perecent) and 1.6 g. (0.01 mole) of m-phenylene diisocyanate and few crystals of triethylene diamine and 40 ml. of hexane was placed into a dry flask, equipped with magnetic stirrer, thermometer, condenser and drying tube.

The mixture was allowed to stir for 4 hours at 50 to 60C. At the end of this time the reaction mixture contained an insoluble organic material.

This material was separated and the trace amount of solvent stripped under reduced pressure. A viscous liquid weighing 1.8 g. was obtained. The IR. indicated that the desired product was obtained.

EXAMPLE XI Preparation of 2,2-bis[3,3-di(t-butylperoxy)butoxy] propane A mixture of 21.0 g. (0.08 mole) of 3,3-di(tbutylperoxy)butanol (96.6 percent), 4.2 g. (0.04 mole) of 2,2-dimethoxypropane, 25 ml. of benzene and 0.002 g. of p-toluensulfonic acid were combined and the mixture was distilled under atmospheric pressure. When 13 ml. of distillate boiling from 57 to 59C. was collected, the distillation was stopped.

The pot residue was cooled down to 23 to 25C. and neutralized with anhydrous Na CO The mixture was filtered and the remaining solvent evaporated under reduced pressure. A liquid weighing 19.2 g. was obtained. The [.R. indicated that the desired product was prepared.

EXAMPLE Xll Preparation of Bis(2[ l ,3-dimethyl-3-(t-butylperoxy)butoxycarboxamido]ethyl) fumarate A mixture of 4.2 g. (0.02 mole) of l,3-dimethyl-3-(tbutylperoxy)-4-pentanol and 2.5 g. (0.01 mole) of bis(2-isocyanoethyl) fumarate and ml'. of hexane was placed into a dry flask equipped with magnetic stirrer, thermometer, condenser and drying tube.

The mixture was allowed to stir for 8 hours at 50 to 60C. At the end of this period the reaction mixture contained an insoluble organic material.

This material was separated and the trace amounts of solvent stripped under reduced pressure.

A viscous liquid weighing 5.2 g. was obtained. The IR. indicated that the desired product was obtained.

EXAMPLE XIII Crosslinkable Compositions A mixture of the desired polymeric material and 0.01 mole of the difunctional coupled compound is blended together on a standard roll mill, such as used in the rubber industry. The mixture is removed from the roll mill and a portion is placed in a press mold andheat cured at a determined temperature for a period of 20 minutes.

The slabs are permitted to cool down and mature at room temperature for 24 hours. The mature slabs were then cut into dumbell shaped samples and tested for tensile strength on an Instron Tensile Tester, following ASTM procedure as described in D412-61T Tension Testing of Vulcanized Rubber or'the crosslinking in the case of polyethylene is determined by thesolvent extraction procedure. In addition to the .polymerperoxide mixture, the crosslinkable mixture, may contain co-agents such as sulfur, promoters, fillers, and re- ""14 inforcing materials. Desirablefillers are carbon black, titanium dioxide, calcium silicate and alkaline earth metal carbonates.

In Table I the crosslinking ability of the coupled cornpounds of our invention in polyethylene are compared to a hydroxy-containing peroxide and todifunctional peroxides. Tables'll, III, and IV show the versatility of the product of our invention in urethane rubber, ethylene-propylene rubber and silicone rubber.

From the table'it is obvious that the coupled compounds of our invention are more efficient than the hydroxy containing peroxide that-they were derived from. This test also showsthat the coupled compounds are significantly more efficient at equal molar equivalents than other difunctional peroxides that are commercially used to crosslink polyethylene.

The urethane rubber charge without peroxide has 0 to 100 psi 300% modulus.

Table I CROSSLINKING OF POLYETHYLENE The polyethylene used for this test was a low density polyethylene called Bakelite DYNH-l, having the following physical properties:

Melt index (ASTM Test D-1238) 190C. 2.0g./10 min.

Density (ASTM Test D4505) 0.919

The crosslinking test was carried out at 340 and 375F. for 30 minutes.

(I) The percentage crosslinking was determined by extraction of the erosslinked sample with refluxing xylene. In all cases the polyethylene charge was 100% extractable before crosslinking. (2) Based on number of active oxygens per mole.

Table II VULCANIZATION OF URETHANE RUBBER FORMULATION Genthane-S (1) 100 parts H.A.F. Carbon Black (2) parts Stearic acid 0.2 parts The cure was carried out with 0.010 mole equivalent of peroxide at 340F. for minutes.

. (psi) (psi) (psi) Peroxides 300% Modulus Ult. Tensile Elongation Di[1,3-dimethyl-3-(t-butylperoxy)butyl] 2091 4512 493 carbonate (Examples I. II, and III) Di[ l.3-dimethyl-3-(t-butylperoxy)butylI 1472 4167 575 suecinate (Example VII) Ethylene bis[ l,3-dimcthyl-S-(t-butylperoxy) 2419 3502 375 butyl carbonatel (Example VIII) (1) (ienthane-S is a designation given to one of the polyurcthancclastomcrs developed by The General Tire & Rubber Company. having the following properties:

Mooney Viscosity (ML4' 212F.) 10

Specific Gravity 1.19

(2) H.A.F. Carbon Black is a high abrasion furnace black.

Table III VULCANIZATION OF ETHYLENE-PROPYLENE RUBBER FORMULATION EPR-404 (1) 100 parts S.R.F. Carbon Black (2) 60 parts Sulfur 0.33 parts Peroxide 0.010 mole equivalent Cure Time 30 minutes Cure Temperature 340F.

(P 1 (p (p Per xid 300% Modulus Ult. Tensile Elongation Di[ l,3-dimethyl-3-(t-butylperoxy)butyl] 1004 2118 567 carbonate (Examples 1, II, and III) Di[ 1 ,3-dimethyl-3-(t-butylperoxy)butyl] 715 2096 710 succinate (Example VII) Ethylene bis[1,3-dimethyl-3-(t-butylperoxy) 1089 2232 552 butyl carbonate] (Example VIII) (1) E.P.R.404 is an ethylene-propylene copolymer elastomeric material manufactured by Enjay, having specific gravity g/cc 0.86 Mooney Viscosity at 212 "F. (8 minutes) 40 (2) S.R'.F. Carbon Black is a semire inTorceinent furnace carbon black manufactured by Cahot Corp.

Without peroxide ethylene-propylene rubber copolyof styrene polymerized styrene 1.65 faster at 115C.

mer has a 300 percent Modulus of 0 to 100 psi.

peroxy)butyl] carbonate (Examples 1, II. & Ill) (1) Silicone Rubber-404 is a general purpose reinforced silicone gum manufactured by General Electric.

The silicone rubber charge without peroxide has a 300 percent modulus of 0 psi.

EXAMPLE XIV This example illustrates the use of coupled peroxides of present disclosures as initiators of vinyl monomer than the thermal polymerization rate when no polymerization initiator is present.

EXAMPLE XV Curing An Unsaturated Polyester-Styrene Resin With Coupled Peroxide An unsaturated polyester resin was made by reacting maleic anhydride (1.0 mole), phthalic anhydride (1.0 mole), and propylene glycol (2.2 mole) until an acid number of 45-50 was obtained. To this was added hydroquinone at a 0.013 percent concentration. Seven parts of this unsaturated polyester was diluted with 3 parts of monomeric styrene to obtain a homogeneous blend having a viscosity of 13.08 poise and a specific gravity of 1.14. To 20 g. of this blend was added the 0.2

g. of the desired coupled peroxide and the resulting composition placed in a constant temperature bath at 1 15C.

The internal temperature was recorded as function of time. The following results were obtained with some of the coupled compounds (Table V):

Table V S.P.l. EXOTHERM AT 115C. 21% CONCENTRATION 1N POLYESTER RESIN PREPARED 1N EXAMPLE VIII Gel Time Cure Time Peak In Barcol Peroxides In Min. Min. F Hardness Di[ 1 ,3-dimethyl-3-(t-butylperoxy)- 9.5 11.1 455 butyl] carbonate (Examples 1,11, and Ill) l Ethylene bis]1,3-dimethyl-3-(t-butyl- 10.8 12.8 450 45 peroxy)butyl carbonate] (Example VIII) Di[2-(t-butylperoxycarbonyl)ethyl] 7.1 8.5 450 45 carbonate (Example V) polymerization. Compound [B] (from Example V) at a concentration of 5 X 10 4 moles per diciliter of styrene, polymerized styrene at 100C. at a rate of 6.20 X 10' moles per liter per minute. When no initiator is present, the thermal polymerization of styrene at 100C. proceeds at a rate of 2.82 X 10* moles per liter per minute. Compound [A] (from Examples 1, II, and III) at a concentration of 5 X 10' moles per diciliter Without an initiator, no cure of the resin blend occured after more than 30 minutes at l 15C.

EXAMPLE XVI Half-life Comparisons of Coupled and Uncoupled Hydroxy-Peroxides (Carried out in Benzene at 0.1 molar concentrations) Peroxide ty hours C.)

(3113 (lJHa 13.6 (115 0.). CHa(FCHz-|COH O H O C a)a 2-methy1-2-(t-butylperoxy)-4-pentanol.

(3H3 (3H3 1 fl) 26.8 (115 0.). CHaCCH2C-O C 1 H O C Hz) a 2 Di[1,3-dimethy1-3-(t-butylperoxy)butyl1carbonate (Examples I, II, and III).

CH: O 13.0 (100 (1.).

OHr-CeO O-CCH2CH2OH t-Butylperoxy 3-hydroxypropionato.

D1[2-(t-butylperoxycarbonyl)ethyHcarbonate (Example V).

matic having 6-12 carbon atoms; d..R is aliphatic or cycloaliphatic, each having 4-10 carbon atoms and the carbon atom joined to the peroxyoxygen atom is a tertiary carbon atom;

e. R, is aliphatic having 1-10 carbon atoms or cycloaliphatic having 3-12 carbon atoms;

f. R is lower alkyl, cycloalkyl, aralkyl, aryl, alkoxy,

cycloalkoxy, aralkoxy, or aryloxy;

g. R is H or lower alkyl;

h. Y is the diradical O, S, or NR j. R is an aliphatic diradical having l-10 carbon atoms or a cycloaliphatic diradical having 3-12 carbon atoms;

k. R is an aliphatic diradical having 1-10 carbon atoms, cycloaliphatic diradical having 3-12 carbon atoms, aromatic diradical having 6-12 carbon atoms, or araliphatic diradical having 7-16 carbon atoms;

1. R is selected from R, YR Y, R C(=O)YR YC(- m. R, and R are selected from H, alkyl of 1-10 carbons and cycloalkyl of 3-12 carbons and, when R is H, R can also be aryl of 6-12 carbons, and R and R when taken together form alkylene of 2-1 1 carbons.

2. The process of claim 1 wherein said agent is di[ 1,-

3-dimethy1-3-(t-buty l-p roi fibutyl] carbonate. 

1. IN THE PROCESS OF CROSSLINKING POLYETHYLENE USING AS THE CROSSLINKING AGENT A FREE RADICAL AFFORDING COMPOUND, THE IMPROVEMENT WHICH COMPRISES USING AS SAID AGENT A PEROXIDE OF THE FORMULA R-W-R'' WHERE: A. W IS SELECTED FROM -C(=O)-, -C(=O)R4C(=O)-,
 1. R4 IS SELECTED FROM R4, YR3U, R3C(=O)YF3YC(=O)R3, YR3YC(=O) YR3YC(=0)YR3Y, (=0) YR3Y, YR3C(=0) YR3C(=O) YR3Y, YR3C(=0)YR3YC(=O)R3Y, YR3UC(=O)YR3Y, YR3YC(=O)R3Y AND YR3YYR3Y; AND M. R7 AND R8 ARE SELECTED FROM H, ALKYL OF 1-10 CARBON AND CYCLOALKYL OF 3-12 CARBON ATOMS AND, WHEN R7 IS H, R8 CAN ALSO BE ARYL OF 6-12 CARBONS, AND R7 AND R8 WHEN TAKEN TOGETHER FORM ALKYLENE OF 2-11 CARBONS.
 2. The process of claim 1 wherein said agent is di(1,3-dimethyl-3-(t-butyl-peroxy)butyl) carbonate. 